Mono-sec-alkylexlenes by alkylation



Aug. 20, 1957 D A, MccAULAY ETAL 2,803,683

MONO-SEC-ALKYLXYLENES BY ALKYLATION original Filed oct. 26, 1953 www QM.

ATTORNEY United States Patent() MoNo-sEc-ALKYLXYLENES BY ALKYLA'rIoN Original application Cctober Z6, 1953, SerialNo. 388,233,

now Patent No. 2,766,307, dated Catcher 9, 1956. Di-

vided and this application February 21, 1956, Serial No. 566,815

8 Claims. (Cl. Zoll-671) This invention relates to the preparation of monoalkylxylenes by the reaction of an olelin and xylene. More particularly, the invention relates to the preparation of ethylxylenes. Still more particularly the invention relates to the preparation of the symmetrical 1,3,S-ethylxylene.

t This application is a division of our copending application Serial No. 388,238, led October 26, 1953, now U. S. Patent No. 2,766,307.

The commercial polystyrene resins have the disability of a softening point lower than the boiling point of Water. It is known that resins prepared from dimethylstyrene have a softening point higher than the boiling point of water. Ethylxylenes with an ortho arrangement of a methyl and the ethyl group dehydrogenate to methylindenes, which are very difficult to separate from the dimethylstyrene. The methylindenes act as plasticizers and lower the softening point of the polydimethylstyrene; the presence of more than about 6% of these contaminants lowers the softening point of the resin below the boiling point of water. In the prior art processes, this undesirable ortho relationship between a methyl and the alkyl group exists in the major portion of the ethylxylene product.

The development of the hydroperoxide synthesis for phenols has caused a large demand for substituted secondary alkybenzenes. Essentially pure isomers are desired in order to permit the production of phenols of specific characteristics. 1,3,5-isopropylxylene is of particular interest in this synthesis.

It is an object of this invention to alkylate xylenes with olens to produce preferentially monoalkylxylenes, which contain predominantly 1,3-dimethyl-S-alkylbenzene. Another object of our invention is to produce ethylxylenes containing a predominant amount of 1,3,5-ethylxylene by ethylating xylenes. Still another object is to prepare essentially pure 1,3,5-ethylxylene by ethylating xylenes. A further object is the preparation of 1,3,5-secondary alkylxylenes by alkylating xylene. A particular object is the preparation of 1,3,5-isopropylxylene. Yet another object is the preparation of 1,3,5-tert-butylxylene. Other objects will be apparent in the detailed description.

It has been found that by the use of liquid HF-BF3 catalyst under controlled conditions, each of the xylene isomers or mixtures thereof can be readily aikylated with ethylene, propylene, butene-l, butene-2 and isobutylene to produce preferentially monoalkylxylenes.

The feed to the process comprises any one of the three xylene isomers or mixtures thereof. ln the presence of HF-BFg agent, olens alkylate benzene and toluene very readily; therefore, the presence of more than apice preciable amounts of benzene and toluene should be avoided.

The acid phase can dissolve a fair amount of paralins, for example, the xylene feed may contain as much as 3 volume percent of paraflns `Without forming a separate hydrocarbon phase (when at least about l mol of BFs is present per mol of xylene charged). The presence of a hydrocarbon phase, i. e., rallinate phase, as not desirable because some of the xylene is withdrawn from the acid phase and the yield of `alkylxylene is decreased and the product distribution is shifted from the desired maximum of 1,3,5-alkylxylene.

Under the conditions of the process, ethylbenzene is rapidly converted to mainly triethylbenzene, ethylxylene, and dialkylethylbenzene. These products boil well above the desired monoalkylxylene and may be separated therefrom by distillation. When the olefin used is ethylene, it may be possible to tolerate large amounts of ethylbenzene in the feed; a suitable feed is the Cs aromatic hydrocarbon fraction obtained by extractive distillation of hydroformate or platformate, i. e., naphtha obtained by the catalytic reforming of virgin naphtha in the presence of hydrogen, which fraction contains about 2-3% of paraiiins and slight amounts of oleiins and C9 aromatic hydrocarbons.

Liquid xylenes react with EP3 and liquid HF to form a complex containing l mol of BFS per mol of xylene and also, probably, l mol of HF per mol of xylene. Alkylxylenes also form a complex with BFS and HF. These complexes are very soluble in liquid HF. It is necessary in the process that sulicient liquid HF be present to dissolve all the complex formed. `The presence of liquid HF in excess of this amount is desirable. Thus the amount of liquid HF should be between about 3 rnols per mol of xylene present in the feed and about 50 mols. It is preferred to use between about 5 and 20 Inols of liquid HF. Put in another way, the amount of liquid HF used may be between about to about 40() volume percent based on xylene charged.

The process must be carried out under substantially anhydrous conditions. The liquid HF used must be substantially anhydrous, that is, the liquid HF should not contain more than about 2-3 of water.

The amount of BFS used in the process may range from about 0.1 mol per mol of xylene (a catalytic amount) to about 5 or more mols. When a mixture of alkylxylene isomers is a satisfactory product, at least about 0.4 mol of BF3 per mol of xylene charged should be used.

In order to obtain better yields of alkylate and to obtain a better alkylate product distribution, the process should be operated under conditions wherein essentially all the feed is dissolved into the acid phase. Some BFs and HF may exist in a separate gaseous phase, but it is preferred to operate at a pressure high enough to dissolve essentially all the BFs in the acid phase. This essential ly single homogeneous phase may be obtained by using at least about l mol of BFS per mel of xylene charged, for example, 0.9 mol.

The production of the desired 1,3,5-alkylxylene is favored by the use of enough BFS to complex all the xylene in the feed. Thus, it is preferred to use between at least 1 and about 3 mols of BFS per mol of xylene charged, for example, 1.5 mols.

The alkylation of xylene with oleiin, in the presence of HF-BFa agent, produces a mixture containing xylene, alkylxylene and polyalkylxylene. The polyalkylate yield may be reduced by operating with an excess of xylene over the amount of oleiin charged. The mol ratioof xylene to olefin should be at least l and a ratio of 20 or more may be used.

With ethylene, it is preferred to use a mol ratio between about 2 and 5, when operatingv at ordinary atmospheric temperatures, i. e., between about Iand about +30 C. At higher temperatures, for example, +60 C., the mol ratio may be only slightly in excess of 1, for example, 1.03.

The distribution of alkylxylene isomers and the relative yields of the various alkylate products is dependent upon both the temperature and the time of contacting. It is believed that a mixture of'isomers is obtained when the olein adds to the xylene to form alkylxylene. Following the .alkylation reaction, an isomen'zation reaction occurs in which the 1,3,5-alkylxylene is preferentially formed. Under suitable conditions of time and temperature, essentially all the alkylxylene present in the acid phase will be the 1,3,5-isomer. Shorter contacting times may be used when a high purity 1,3,5-alkylxy1ene, i. e., about 95%, product fraction is desired.

The permissible temperatures vary markedly with the type of olen used in the process. The oletins usable in the process are selected from the class consisting of ethylene, propylene, isobutylene, butene-l and butene-2. The use of pentenes and higher olelins results in excessive side reactions, such as cracking and rearrangement of the alkyl group. In order to set out the relationship of temperature and time to product distribution, the various oleins are discussed in accordance with the individual characteristics of the alkylate products.

Ethylene alkylation The ethylxylenes undergo cracking reactions and the formation of tars, condensed ring compounds and gases at temperatures above about +135 C. Xylenes undergo a disproportionation reaction at high temperatures. In order to minimize the loss of xylene to trimethylbenzene, the ethylation process should be carried out at a temperature of not more than about +75 C. and preferably below about +65 C.

Low temperatures reduce the rate of formation of 1,3,5- ethylxylene and also alect the rate of alkylation. In general, the contacting time, at `a particular temperature, is dependent upon the desired degree of conversion of the ethylxylene fraction to the 1,3,5-ethylxylene isomer. Temperatures as low as 20 C. or lower can be used if the correspondingly longer time of contacting is tolerable; for example, at 20 C., a time of 20 hours should be used. At about +35 C., a suitable reactionk time is about 5 minutes. When using higher ratios of xylene to ethylene, the preferred temperature is between about +15 `and +35 C., using a time between about 5 minutes and 5 hours, the longer times corresponding to the lower temperatures. Higher temperatures, i. e., +50 to +65 C., have a favorable effect on the yield of ethylxylene at lower xylene to ethylene ratios. Essentially pure 1,3,5-ethylxylene can be produced in very high yield by carrying out the ethylation at about +65 C. for a time of about minutes; at about +50 C., a suitable time is .about 30 minutes.

In general, it is preferred to operate with about the minimum contacting time needed to obtain the degree of 1,3,5-ethylxylene readily obtainable at the particular ternperature of operation.

Propylene, butene-l and butene-Z alkylaton The alkylation of xylene with olelins from the class ucts containing a secondary alkyl group, namely, isopropyl and sec-butyl. These secondary alkylxylenes undergo extensive cracking reactions at temperatures above about C. Condensation reactions proced to an appreciable extent when long contacting times are used at temperatures of about +40 C. and higher; it is desirable to operate at a temperature of not more than about +40 C.

The secondary alkylxylenes isomerize much more readily than the ethylxylenes; therefore, very low temperatures, such as 20 C., may be employed without having to use extremely long contacting times. At 20 C., high purity 1,3,5-secondary alkylx'ylene is obtained when using a time of about 2 hours.

As the temperature is raised, the time of contacting is correspondingly decreased. When the temperature of contacting is about +20 C., the contacting time is between about 5 and 20 minutes. At a temperature of +40 C., the time is between about 1 and 5 minutes; at these higher temperatures, the time of contacting should be as short as practicable in order to decrease the yield of side reaction products, i. e., the time should be as close to about 1 minute as equipment limitations will permit.

It is preferred to operate the secondary alkylxylene production process at a temperature between about 0 and +20 C. for a time between about 5 and about 60 minutes, the longer times corresponding to the lower temperatures.

Isobutylene alkylaton The alkylation of xylene with isobutylene gives products containing a tertiary butyl group. These tert-butylxylenes undergo extensive cracking and condensation reactions at temperatures of about +25 C. In order to substantially avoid these side-reactions, the temperature of operation should be maintained below about +15 C. The yield of the desired 1,3,5-tert-butylxylene is improved by operation at temperatures of not more than about 0 C., for example, 20 C. The tert-butyl group is so active that temperatures as low as about 75 C. may be used without requiring extremely long contacting times.

When operating at a temperature of about +15 C., Very short contacting times should be used-between about 1 minute and 5 minutes. At 0 C., the contacting time maybe between about 5 and 30 minutes. The lower the temperature of contacting, the longer the permissible contacting time, without significant adverse eiect on the yield of the 1,3,5-tert-butylxylene.

EXAMPLES The results obtained by the invention are illustrated by several experimental examples and one using HF alone as the catalyst. The results of these experiments are presented in Tables I and II. In order to illustrate the experimental procedure, runs 5 `and 7 are set out in detail below.

VRun 5.-The runs were carried out in a l570 ml. carbon steel autoclave fitted with a 1725 R. P. M. stirrer. 3.02 mols of m-xylene were added to the reactor; this was followed by 23 mols of liquid HF (150 volume percent on xylene). BFa was pressured into the reactor from a small cylinder. A total of 4.5 mols of BFS were added,

which amounted to an uncorrected BFS/xylene ratio of 1.5. At the reaction temperature of +20 C., the pressure in the reactor was p. s. i. a. Taking into account the free space in the reactor, the partial pressure of HF and the solubility of BF3 at this temperature and pressure, the free BFS was calculated to be about 1.5 mols. Thus the corrected BFS/xylene was 1.0, i. e., the theoretical for the complexing of al1 the meta-xylene.

The total; productv distribution in this run was as follows:

Ethylene was added to the contents of the reactor over in run Birch ,5-ethylxylene as` given by Insofar as the analytical methods used could determine, no hydrocarbons containing more than 12 carbon ato were present in the product.

The properties of the total ethylxylene product 5 and the properties of 1,3

Birch et a1., JACS, 71, 1362 (April 1949), are

B. P., O

Sp. Gr

a period of 5 minutes; 1.21 mols were added for a The ask was allowed to warm to room temperature. The contents were transferred to a separating funnel Where the supernatant hydrocarbons-displaced from 6 their complexes by the Water-Were separated from the aqueous acid phase. The hydrocarbons were Washed with dilute aqueous ammonium hydroxide to remove traces of HF and BFa. The hydrocarbons were fractionated through a column of 30 theoretical plates. The distilla- 70 tion separated the product into groups according to number of carbon atoms; the composition of each group was determined by a combination of ultraviolet, and infrared absorption, refractive index, boiling point and specic gravity.

Run ,7.-Inf this run, the# feed-consisted of. 2.11' mols The amountof liquid HF used was 150 volume'percent based-son'total of m-xylene and 0.92 mols of p-xylene.

xylene feed. Enough BFs was added to the react-r to give an uncorrected BFs/total'xylene-'ratio of 1.5. The pressure in the reactor at the reaction temperature'ofv 25 C. was 160 p. s. i. a. The correctedBFs/total xylene was,1.0, i. e., the theoretical for'the complexing ofboth` scribed in run 5. The total product distribution intheV TUI). WaSI Hydrocarbon Percent ntl-xylene p-xylene 1,3,2-ethylxylene 1,4,3-ethy1xylene O12 aromatics The properties of the total ethylxylene .product in run 7 are:

In Table l, run l shows the use of liquid HF as the catalyst for the ethylation of meta-xylene. In this run, 58% of the ethylene reacted to form aromatics containing three or four ethyl groups (C14 and C16 aromatics). Of the ethylxylene produced, almost 80% was 1,3,4-ethylxylene which has a methyl group and the ethyl group in ortho relation. Run 2 is substantially identical with run l except that 0.74 (corrected) mol of BFS was added per mol of xylene. In this run, `no C16 aromatics were produced. The directional effect of the BF3 on the ethylxylene distribution is shown by the'fact that the'desired 1,3,5-ethylxylene represents-about 60% of the total-ethylparticularly noteworthy in view. of `run 4- where theBFswas present in an amount only slightly under the theoretical amount; here the ethylxylenes contained about 30% of LSA-ethylxylene; this effect ofV the single phase At the Yend of 'this'm amount of 'xylenefand' ethylene was present: However, in rum-l0, .whereina slight excess of .xylene was-present,

only.about 6% of the. alkylate consistsV of `the Vdiand.

Thesesruns'show the marked benecialVv triethylxylenes. eiect onyield of -the presence of even slightamountsof excess xylene when operating at higher temperatures.

Run ll'illustrates the'propylation of m-xylene. The alkylate contained 81% of isopropylx-ylene-all of which wasfiwithin analytical error,V the 1,3,5-isopropy1xylene 1 isomers The higher boiling fraction iconsisted of a wide boiling range mixture of alkylbenzenes and condensation f products.

Run l2 illustrates -the isobutylation of m-xylene. Herein an appreciable yield of materials believed to be polyl. isobutyleneswas-formed which is not considered in the The identiiiable reaction product mixture reported. alkylate consists of the 1,3,5-tert-butylxylene. Almost an equal quantity of alkylbenzenesand condensation products were'formed. A shorter time would have'increasedthe yield of the 1,3,5-tert-butylxylene.

ILLUSTRATIVE EMBODIMENTr The accompanying drawing-shows Vone embodiment of our process for the production of high purity 1,3,5-ethyli xylene by the ethylation of meta-xylene. It is to be understood that this 'embodiment is shown for purposes of illustration-onlyv and that many other Variations of `our process can beV readilydevised by those ,skilled in the art.VA

In'this illustration, :the charge consists of substantially pure meta-xylenefrom-a source 11. However, the charge could be amixture of meta-xylene, para-xylene-andV ethylhomogeneous system is all the-more striking-since t-he-V amount of ethylxylene produced Ywas al'JQutjthe same iny each run.

Runs 6 and 7 used a mixed xylene feed. In run 6, theV benzene, ortho-xylene `or a mixture of meta-, ortho-, paraxylene'andethylbenzene; Meta-xylene from source .'11 is passed through line 12 into line 13. Liquid HF'fro'm source 14 is passed through valved line 16, through line 17,; and through line 18 into line A13. The amountof liquid HF used here is l0 mols per mol based on xylene charged. BF3 from source 19 is passed throughvalved line 21, through line 22 and into line 18 where it is commingled with the liquid HF. The amount of BFS used in this example is `1.5 mols' of BF3 per mol of xylene charged in order to insure the complexing of all xylene charged and the'formation of a single phase homogeneous system. The liquid HF-BFa in l'line V18 joins the xylene in line 13 and the whole passes into mixer-23.

Mixer 23 may be'any form of device that provides ,thorough agitation, for example, an orice mixer. The

reaction of the BF3, HF and metaxylene to form the complex is exothermic and mixer 23 is provided with a cooling coil 24 to enable the temperature of the'reaction mixture. to be controlled.

Ethylene from source 25 is passed through valved-line 26 into line 27 where it meets the homogeneous system passing out of vmixer 23. The amount of ethylene used in this example is l mol per 2.5 mols of xylene. Reactor 23 is provided witha coil 29 which 'is used to maintain paraxylene alkylated to form the 1,4,3-ethylxylene isomer-.M

The ethylbenzene in the feed alkylatedY to triethylbenzene4 rather than to diethylbenzene. In run 7, the 1,4;3-ethyl1 xylene-resulting from the ethylation of para-xylene has been substantially completely isomerized to 1,3,5-'ethylxylene; this result is believed t'o be primarily the effect of the single phase homogeneous system. In run 7, the

into stripper 33.

and fl 0, no detectable amounts of any ethylxylene somer,.

other Ithan the desired` lf,3,5-isorner, werepresent.n In.

run 9, 22% of the alkylateY was madeV up of the "di-"and tri-ethylxylenes; in this'run, slightly less than an equimolar the temperature of the-reaction mixture relatively'f-constant. about +20" C. The reactants are held in reactor 28 for a time sucient to obtain ethylation and conversion of the ethylxylenes into the'v desired symmetrical 1,3,5-ethyl`- xylene. In this example, the reaction time is l5 minutes.`

From reactor Zfthe homogeneous system is passed intoline 30 and on into`cooler`31.` Cooler 31 is neededV- only when very high reaction temperatures are usedgthe' reaction mixture is cooled quickly'in order to eliminate disproportionation of the xylene.A

From cooler;31, the' mixture isv passed through line 32' In stripper 33, the' HF'and B133 are removed Vfrom the hydrocarbons. In order'to avoid the formation of undesirable products through disproportionation and cracking, the nremoval of theHF'and BFS is carried out under vacuum; the stripping operationis Temperature in the reactor in this'exampleisfacilitated by the use of a stripping agent; butane is introduced into stripper 33 through line 34.

The HF and BFa are passed out of stripper 33 through line 36, through vacuum pump 37 and line 38 into condenser 39. In condenser 39, the butane and HF are liquied and are passed through line 41 into settler 42. The free BF3 is passed out of settler 42 through lines 43 and 44 to line 22 for reuse in the process. The liquid butane is passed out of settler 42 through line 46 and may be returned to line 34 for reuse in the stripping operation. The liquid HF, saturated with BFa, is passed out of settler 42 through valved line 47 into line 17 and may be reused in the process.

The hydrocarbons are passed out of stripper 33 through line 51 through heater 52 and line 53 into fractionator 54. Fractionator 54 is provided with a reboiler 55, which reboiler in conjunction with heater 52 provides the heat necessary to separate the hydrocarbons into the respective fractions. The unreacted xylene is taken overhead from fractinator 54 through line 56 and is condensed in cooler 57. The xylene is recycled to the reactor by way of valved line 58 and line 59 and line 12.

The ethylxylenes are withdrawn from an upper part of fractionator 54 by way of line 61 and are passed to storage not shown. The ethylxylenes in this example consist of about 95% 1,3,5-ethylxylene and the remainder the 1,3,4- and 1,3,2-ethylxylene configurations.

The higher boiling C12 and any C14 aromatic fraction is withdrawn from the bottom of fractionator 54 by way of line 64 and are passed to storage, not shown.

One embodiment of the process has been described wherein substantially pure meta-xylene has been the feed material. A mixture of meta-xylene, ortho-xylene and para-xylene can be used with only one variation from the above conditions. For the mixed xylene feed, a reaction time of about 2 hours is used in order to isomerize the mixed ethylxylenes to the 1,3,5-ethylxylene.

When the feed to the process contains ethylbenzene, in addition to xylenes, no change in operating conditions need be made. The ethylbenzene reacts to form triethylbenzene and ethylxylene. The triethylbenzene is passed out of the system with the higher boiling C12 and C14 fractions.

When no appreciable demand exists for by-product diethylxylene and triethylxylene, the process is carried out at higher temperatures. The xylene to ethylene ratio is 1:1 and reactor 28 is maintained at +65 C.; the reaction time is 8 minutes. Essentially pure 1,3,5-ethylxylene is withdrawn by way of line 61. In this method of operation, about of the alkylate is the 1,3,5-ethylxylene.

Thus having described the invention, what is claimed is:

1. A process for the preparation of high purity 1,3,5- secondary alkylxylene, which alkyl group is selected from the class consisting of isopropyl and sec-butyl, which process comprises (1) contacting, under substantially anhydrous conditions, a feed consisting essentially of at least one xylene isomer with at least about 1 mol of BFs and between about 3 and 50 mols of liquid HF, respectively, per mol of xylene in said feed, to forman essentially single phase homogeneous system, (2) adding an olen selected from the class consisting of propylene, butene-l and butene-2, in a mol ratio of xylene to olefin of at least about 1, while (3) maintaining the reaction zone at a temperature of between about 20 C. and about |40 C. for a time between about 1 minute and about 2 hours, the longer times corresponding to the lower temperatures (4) covering HF and BFs from a hydrocarbon product and (5) recovering from said product a secondary alkylxylene fraction consisting of high purity 1,3,5-secondary alkylxylene.

2. The process of claim 1 wherein said temperature is between about 0 and [-20" C. and said time is between about 5 and 60 minutes.

3. The process of claim 1 wherein said feed is p-xylene.

4. The process of claim 1 wherein said feed is o-xylene.

5. The process of claim 1 wherein said olen is propylene.

6. The process of claim 1 wherein said olen is butene-1.

7. The process of claim 1 wherein said olefin is butene-2.

8. The process of claim 1 wherein said olefin is a mixture of butene-l and butene-Z.

References Cited in the le of this patent UNITED STATES PATENTS 2,423,470 Simons July 8, 1947 2,713,600 Langlois July 19, 1955 2,740,819 Kirkland Apr. 3, 1956 2,766,307 McCaulay et al. Oct. 9, 1956 

1. A PROCESS FOR THE PREPARATION OF HIGH PURITY 1,3,5SECONDARY ALKYLXYLENE, WHICH ALKYL GROUP IS SELECTED FROM THE CLASS CONSISTING OF ISOPROPYL AND SEC-BUTYL, WHICH PROCESS COMPRISES (1) CONTACTING, UNDER SUBSTANTIALLY ANHYDROUS CONDITIONS, A FEED CONSISTING ESSENTIALLY OF AT LEAST ONE XYLENE ISOMER WITH AT LEAST ABOUT 1 MOL OF BF3 AND BETWEEN ABOUT 3 AND 50 MOLS OF LIQUID HF, RESPECTIVELY, PER MOL OF XYLENE IN SAID FEED, TO FORM AN ESSENTIALLY SINGLE PHASE HOMOGENEOUS SYSTEM, (2) ADDING AN OLEFIN SELECTED FROM THE CLASS CONSISTING OF PROPYLENE, BUTENE-1 AND BUTENE-2, IN A MOL RATIO OF XYLENE TO OLEFIN OF AT LEAST ABOUT 1, WHILE (3) MAINTAINING THE REACTON ZONE AT A TEMPERATURE OF BETWEEN ABOUT-20*C. AND ABOUTT +40*C. FOR A TIME BETWEEN ABOUT 1 MINUTE AND ABOUT 2 HOURS, THE LONGER TIMES CORRESPONDING TO THE LOWER TEMPERATURES (4) COVERING HF AND BF3 FROM A HYDROCARBON PRODUCT AND (5) RECOVERING FROM SAID PRODUCT A SECONDARY ALKYLXYLENE FRACTION CONSISTING OF HIGH PURITY 1,3,5-SECONDARY ALKYLXYLENE. 